First measurements of OH-C exchange and temperature-dependent partitioning of OH and halogens in the system apatite - silicate melt

We present the first integrated study of carbonate, hydroxyl, fluoride, and chloride ion partitioning in the apatite-melt system. We determined volatile partitioning behavior between apatite and silicate melt for both haplobasaltic andesite and trachyte bulk compositions at 0.5–1 GPa and 1250°C using the piston-cylinder apparatus. All volatile species were analyzed directly in both apatite and glass using secondary ion mass spectrometry (SIMS) and electron probe microanalysis. Distribution coefficients for OH-halogen exchange are similar to those from previous studies, and together with literature data, reveal a significant log-linear relationship with temperature, while the effects of pressure and melt composition are minimal. Meanwhile, halogen-free experiments generate very high C contents (up to 5000 ppm) in apatite. Stoichiometry calculations and infrared spectra indicate that this C is mainly incorporated onto the channel volatile site together with hydroxyl. In halogen-bearing experiments, apatite crystals contain significantly lower C (≤500 ppm), which may be partly incorporated onto the phosphate site while the channel volatile site is filled by OH+F+Cl+C. Our experiments give the first constraints on H2O-CO2 exchange between apatite and silicate melt, with a KD of 0.355 ± 0.05 for the trachyte and 0.629 ± 0.08 for the haplobasaltic andesite. The new constraints on the temperature-dependence of partitioning will enable quantitative modeling of apatite-volatile exchange in igneous systems, while this new partitioning data and method for direct, in situ analysis of C in apatite mark a significant advance that will permit future studies of magmatic C and other volatiles. This has a broad range of potential applications including magmatic differentiation, fractionation, and degassing; quantification of volatile budgets in extraterrestrial and deep earth environments; and mineralization processes

Volcanic spherules condensed from supercritical fluid in the Payenia volcanic province, Argentina

Spherules can be formed by high temperature processes during volcanic eruptions, lightning strikes and meteorite impacts. Here we report four different types of spherules and spheroidal particles associated with tephra deposits from two separate volcanic fields in the southern Payenia province of Argentina. These silicate and carbonate spherules represent <0.01 % of the sampled material with individual spherules <200 µm in size. Thirty particles have been imaged, only the transparent spherules are smooth, perfect spheres. Other morphologies include ellipsoids and aggregated dumbbells, and the spheroids are hollow or solid. Major-element analyses show that the spherules and spheroids have silica-rich, iron-rich, carbonate and basaltic compositions. Chemical analysis of the carbonate spheroids shows some variability in trace element content between the cores and rims suggesting element mobility and loss towards the margins. All analysed carbonate spheroids have elevated Sr/Y, La/Y and La/Ce, outside of the range of sedimentary carbonate. All four spherule types are considered volcanic in origin, with the excess CO2 required for the formation of carbonate spherules potentially sourced from basement lithologies. Based on major- and trace-element analyses we conclude that the silica-rich and carbonate spherules formed by instantaneous condensation from supercritical CO2-rich hydrous fluids saturated with dissolved silicates

Using zircon in mafic migmatites to disentangle complex high-grade gneiss terrains – Terrane spotting in the Lewisian complex, NW Scotland

This research was part of SF’s PhD studies, and he acknowledges a 600 Year Anniversary Scholarship from the University of St Andrews. Analyses were funded through grants with EIMF (IMF545/1114) and NIGL (IP-1473-1114). Fieldwork was funded by NERC grant NE/J021822/1 to PAC. TEJ acknowledges funding from Australian Research Council Discovery Project DP200101104 and support from the State Key Laboratory for Geological Processes and Mineral Resources, China University of Geosciences, Wuhan (Open Fund GPMR201903). PAC acknowledges support from Australian Research Council grant FL160100168. CJH acknowledges support from Leverhulme Trust grants RPG-2015-422 and EM-2017-047\4.The zircon record of complex high-grade gneiss terrains is key to interpreting their tectonothermal evolution. Typically, such studies focus on zircon-rich, felsic rocks, which commonly have a complicated (partial melting, inheritance, partial dissolution, and reprecipitation) zircon record. Here we show that metamorphosed mafic rocks and their retained partial melts (i.e. in situ leucosomes) provide a record of the evolution of crustal blocks that is simpler and easier to interpret. We apply our method to the Archaean high-grade gneisses of the iconic Lewisian complex of NW Scotland and use it to test the proposed terrane model that is based largely on zircon geochronology. Our work focusses on the mafic migmatites of the central region, where we identified the long-established metamorphic age clusters of ca. 2.75 Ga and 2.5 Ga, as well as ca. 2.85 Ga protolith ages. A key finding is that these ages are recognised across both putative terrane blocks of the central region previously proposed to record different tectonothermal histories. Our oldest (inherited) ages are similar to those within other blocks outside the central region. Thus, all these blocks likely share a common pre-metamorphic history, questioning the validity of the terrane model for the Lewisian complex. We demonstrate that mafic lithologies provide a powerful tool for identifying key stages in the polyphase evolution of metamorphic complexes that typify Earth’s earliest rock records and offer additional context for assessing Earth’s geodynamic evolution.PostprintPeer reviewe

Listening In on the Past: What Can Otolith δ18O Values Really Tell Us about the Environmental History of Fishes?

Oxygen isotope ratios from fish otoliths are used to discriminate marine stocks and reconstruct past climate, assuming that variations in otolith δ18O values closely reflect differences in temperature history of fish when accounting for salinity induced variability in water δ18O. To investigate this, we exploited the environmental and migratory data gathered from a decade using archival tags to study the behaviour of adult plaice (Pleuronectes platessa L.) in the North Sea. Based on the tag-derived monthly distributions of the fish and corresponding temperature and salinity estimates modelled across three consecutive years, we first predicted annual otolith δ18O values for three geographically discrete offshore sub-stocks, using three alternative plausible scenarios for otolith growth. Comparison of predicted vs. measured annual δ18O values demonstrated >96% correct prediction of sub-stock membership, irrespective of the otolith growth scenario. Pronounced inter-stock differences in δ18O values, notably in summer, provide a robust marker for reconstructing broad-scale plaice distribution in the North Sea. However, although largely congruent, measured and predicted annual δ18O values of did not fully match. Small, but consistent, offsets were also observed between individual high-resolution otolith δ18O values measured during tag recording time and corresponding δ18O predictions using concomitant tag-recorded temperatures and location-specific salinity estimates. The nature of the shifts differed among sub-stocks, suggesting specific vital effects linked to variation in physiological response to temperature. Therefore, although otolith δ18O in free-ranging fish largely reflects environmental temperature and salinity, we counsel prudence when interpreting otolith δ18O data for stock discrimination or temperature reconstruction until the mechanisms underpinning otolith δ18O signature acquisition, and associated variation, are clarified

The KD Sr/Ca in cultured massive Porites spp. corals are reduced at low seawater pCO2

This work was supported by the UK Natural Environment Research Council (award NE/I022973/1) to AAF and NA.Coral skeletal Sr/Ca has valuable potential as a proxy of sea surface temperatures (SSTs). However seawater pCO2 can influence skeletal Sr incorporation and Sr/Ca-SST calibrations derived from present day corals may not be applicable to ancient specimens or older sections of modern corals deposited under lower seawater pCO2 than the present day. In this study we analysed skeletal Sr/Ca in multiple genotypes of massive Porites spp. cultured over a range of seawater pCO2 (from 180 to 750 μatm) and temperature (25°C and 28°C). Multiple linear regression analysis indicates that the Sr/Ca aragonite partition coefficient, KD Sr/Ca is inversely related to seawater temperature and positively related to seawater pCO2 (equivalent to changes in skeletal Sr/Ca of 0.046 mmol mol-1 °C-1 and 0.0002 mmol mol–1 µatm-1 respectively). Applying present day Sr/Ca-SST equations to older coral skeletons growing at lower pCO2 could underestimate seawater temperatures. However KD Sr/Ca vary significantly between some coral genotypes cultured at the same seawater pCO2 indicating that other unidentified processes also influence skeletal Sr/Ca and it is unknown how these processes varied when ancient corals were deposited. We do not observe a significant relationship between KD Sr/Ca and coral calcification rate after combining all coral genotypes to allow identification of the correct KD Sr/Ca to apply to coral records.PostprintPeer reviewe

Assessing sulfur redox state and distribution in abyssal serpentinites using XANES spectroscopy

Sulfur is one of the main redox sensitive and volatile elements involved in chemical transfers between earth surface and the deep mantle. At mid-oceanic ridges, sulfur cycle is highly influenced by serpentinite formation which acts as a sink of sulfur under various oxidation states (S 2 − , S − , S 0 and S 6 + ). Sulfur sequestration in serpentinites is usually attributed to the crystallization of secondary minerals, such as sulfides (e.g. pyrite, pyrrhotite) or sulfates (e.g. anhydrite). However, the role of serpentine minerals as potential sulfur carriers is not constrained. We investigate the distribution and redox state of sulfur at micro-scale combining in situ spectroscopic (X-ray absorption near-edge structure: XANES) and geochemical (SIMS) measurements in abyssal serpentinites from the SWIR (South West Indian Ridge), the Rainbow and the MARK (Mid-Atlantic Ridge, Kane Fracture Zone) areas. These serpentinites are formed in different tectono-metamorphic settings and provide a meaningful database to understand the fate of sulfur during seafloor serpentinization. XANES spectra of serpentinite powders show that the sulfur budget of the studied samples is dominated by oxidized sulfur (S 6 + / S = 0.6–1) although sulfate micro- phases, such as barite and anhydrite, are absent. Indeed, μ -XANES analyses of mesh, bastite and antigorite veins in thin sections and of serpentine grains rather suggest the presence of S 6 + ions incorporated into serpentine minerals. The structural incorporation of S in serpentine minerals is also supported by X- ray fluorescence mapping revealing large areas (1600 μm 2 ) of serpentinite where S is homogeneously distributed. Our observations show that serpentine minerals can incorporate high S concentrations, from 140 to 1350 ppm, and that this can account for 60 to 100% of the sulfur budget of abyssal serpentinites. Serpentine minerals thus play an important role in S exchanges between the hydrosphere and the mantle at mid-oceanic ridges and may participate to S recycling in subduction zones.NERC Deep Volatiles Consortium Grant NE/M000303/

Micro-scale geochemical and crystallographic analysis of Buccinum undatum statoliths supports an annual periodicity of growth ring deposition

The whelk Buccinum undatum is commercially important in the North Atlantic. However, monitoring the ontogenetic age and growth of populations has been problematic for fisheries scientists owing to the lack of a robust age determination method. We confirmed the annual periodicity of growth rings present in calcified statoliths located in the foot of field-collected and laboratory reared whelks using microscale measurements of trace element geochemistry. Using Secondary Ion Mass Spectrometry (SIMS), annual trace element profiles were quantified at 2 μm resolution in statoliths removed from whelks collected alive from three locations spanning the length of the UK; the Shetland Isles (North), the Menai Strait, North Wales (Mid) and Jersey (South). Clear cycles in the Mg/Ca ratio were apparent with minimum values corresponding with the visible dark statolith rings and comparatively higher ratios displayed in the first year of growth. Statoliths from one and two-year-old laboratory reared whelks of known age and life history contained one and two Mg/Ca cycles respectively and demonstrated that the statolith growth ring is formed during winter (February and March). Cycles of Na/Ca were found to be anti-correlated to Mg/Ca cycles, whilst ratios of Sr/Ca were inconsistent and showed an apparent ontogenetic increase, suggesting strong physiological control. Variability in elemental data will likely limit the usefulness of these structures as environmental recorders. The results obtained using SIMS for trace element analysis of statoliths confirms the robustness of the statolith rings in estimating whelk age. μXRD at 2 μm spatial resolution demonstrated the statoliths were wholly aragonitic and thus trace element variation was not the result of possible differences in CaCO3 polymorph within the statolith. Changing XRD patterns along with SEM imaging also reveal an ‘hourglass’ microstructure within each statolith. The validation of the annual periodicity of statolith growth rings now provides a robust and novel age determination technique that will lead to improved management of B. undatum stocks

A comparison of SNARF-1 and skeletal δ11B estimates of calcification media pH in tropical coral

Funding: SIMS analyses were supported by the Natural Environment Research Council, UK (IMF689/0519).Coral skeletal boron geochemistry offers opportunities to probe the pH of the calcification media (pHCM) of modern and fossil specimens, to estimate past changes in seawater pH and to explore the biomineralisation response to future ocean acidification. In this research we grew 2 Stylophora pistillata coral microcolonies over glass coverslips to allow analysis of the pH sensitive dye SNARF-1, in the extracellular calcification medium at the growing edge of colonies where the first aragonite crystals are formed, under both light and dark conditions. We use secondary ion mass spectrometry (SIMS) to measure the boron isotopic composition (δ11B) of the skeleton close to the growth edge after 2 to 3 days of additional calcification had enlarged the crystals until they joined, generating a continuous sheet of aragonite. Mean skeletal δ11B-pHCM estimates are higher than those of by SNARF-1 by 0.35 to 0.44 pH units. These differences either reflect real variations in the pH of the calcification media associated with each measurement technique or indicate other changes in the biomineralisation process which influence skeletal δ11B. SNARF-1 measures directly the pH of the extracellular calcification medium while skeletal δ11B analyses aragonite potentially formed via both extracellular and intracellular biomineralisation pathways. Analysis of a third coral specimen, also growing on a glass slide but with a 5 cm long branch, indicated good agreement between the δ11B value of the apex of the branch and the skeletal growth edge. The tissues overlying both these regions were transparent indicating they had low symbiont densities. This suggests that the biomineralisation process is broadly comparable between these sites and that studies growing corals over glass slides/coverslips provide representative data for the colony apex.Publisher PDFPeer reviewe

Sulfur isotopes of hydrothermal vent fossils and insights into microbial sulfur cycling within a lower Paleozoic (Ordovician‐early Silurian) vent community

This study was supported by a UK Natural Environment Research Council grant (NERC; number NE/R000670/1 to AG). MG is also grateful for support from an Ifremer Postdoctoral Fellowship. Alvinella samples were collected with the help of a NERC Small Grant (number NE/C000714/1 to CTSL). S isotopic analyses were undertaken under NERC Facility awards IP-1755-1117 and IMF672/1118.Symbioses between metazoans and microbes involved in sulfur cycling are integral to the ability of animals to thrive within deep‐sea hydrothermal vent environments; the development of such interactions is regarded as a key adaptation in enabling animals to successfully colonize vents. Microbes often colonize the surfaces of vent animals and, remarkably, these associations can also be observed intricately preserved by pyrite in the fossil record of vent environments, stretching back to the lower Paleozoic (Ordovician‐early Silurian). In non‐vent environments, sulfur isotopes are often employed to investigate the metabolic strategies of both modern and fossil organisms, as certain metabolic pathways of microbes, notably sulfate reduction, can produce large sulfur isotope fractionations. However, the sulfur isotopes of vent fossils, both ancient and recently mineralized, have seldom been explored, and it is not known if the pyrite‐preserved vent organisms might also preserve potential signatures of their metabolisms. Here, we use high‐resolution secondary ion mass spectrometry (SIMS) to investigate the sulfur isotopes of pyrites from recently mineralized and Ordovician‐early Silurian tubeworm fossils with associated microbial fossils. Our results demonstrate that pyrites containing microbial fossils consistently have significantly more negative δ34S values compared with nearby non‐fossiliferous pyrites, and thus represent the first indication that the presence of microbial sulfur‐cycling communities active at the time of pyrite formation influenced the sulfur isotope signatures of pyrite at hydrothermal vents. The observed depletions in δ34S are generally small in magnitude and are perhaps best explained by sulfur isotope fractionation through a combination of sulfur‐cycling processes carried out by vent microbes. These results highlight the potential for using sulfur isotopes to explore biological functional relationships within fossil vent communities, and to enhance understanding of how microbial and animal life has co‐evolved to colonize vents throughout geological time.Publisher PDFPeer reviewe

Volatiles and intraplate magmatism: A variable role for carbonated and altered oceanic lithosphere in ocean island basalt formation

Recycling of material at subduction zones has fundamental implications for melt composition and mantle rheology. Ocean island basalts sample parts of the mantle from variable depths that have been diversely affected by subduction zone processes and materials, including the subducted slab, metasomatising melts and fluids. Resultant geochemical differences are preserved at a variety of scales from melt inclusions to whole rocks, from individual islands to chains of islands. Here we examine a global dataset of ocean island basalt compositions with a view to understanding the connection between silica-saturation, olivine compositions, and halogens in glass and olivine-hosted melt inclusions to reveal information regarding the mantle sources of intraplate magmatism. We find that minor elements incorporated into olivine, although informative, cannot unambiguously discriminate between different source contributions, but indicate that none of the OIB analysed here are derived solely from dry peridotite melting. Nor can differences in lithospheric thickness explain trace element variability in olivine between different ocean islands. We present new halogen (F, Cl, Br/Cl, I/Cl) data along with incompatible trace element data for the global array and encourage measurement of fluorine along with heavier halogens to obtain better insight into halogen cycling. We suggest that Ti-rich silica-undersaturated melts require a contribution from carbonated lithosphere, either peridotite or eclogite and are an important component sampled by ocean island basalts, together with altered oceanic crust. These results provide new insights into our understanding of mantle-scale geochemical cycles, and also lead to the potential for the mantle transition zone as an underestimated source for observed volatile and trace-element enrichment in ocean island basalts